Charge transfer drives anomalous phase transition in ceria
Abstract
Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of -25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2- anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.
- Authors:
-
- Univ. of Science and Technology Beijing (China). Beijing Advanced Innovation Center for Materials Genome Engineering. Dept. of Physical Chemistry. State Key Lab. for Advanced Metals and Materials
- Beijing Inst. of Technology (China). School of Aerospace Engineering
- Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
- Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics
- Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Chemistry
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Science and Technology Beijing (China); Beijing Institute of Technology (China); Chinese Academy of Sciences (CAS), Beijing (China)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); Program for Changjiang Scholars (China); Innovative Research Team in University (China); Program of Introducing Talents of Discipline to Universities (China); Thousand Young Talents Program of China
- OSTI Identifier:
- 1505144
- Grant/Contract Number:
- AC02-06CH11357; 21590793; 21731001; 11572040; IRT1207; B14003; U1501501
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 9; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; electron transfer; structural properties
Citation Formats
Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, and Xing, Xianran. Charge transfer drives anomalous phase transition in ceria. United States: N. p., 2018.
Web. doi:10.1038/s41467-018-07526-x.
Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, & Xing, Xianran. Charge transfer drives anomalous phase transition in ceria. United States. https://doi.org/10.1038/s41467-018-07526-x
Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, and Xing, Xianran. Thu .
"Charge transfer drives anomalous phase transition in ceria". United States. https://doi.org/10.1038/s41467-018-07526-x. https://www.osti.gov/servlets/purl/1505144.
@article{osti_1505144,
title = {Charge transfer drives anomalous phase transition in ceria},
author = {Zhu, He and Yang, Chao and Li, Qiang and Ren, Yang and Neuefeind, Joerg C. and Gu, Lin and Liu, Huibiao and Fan, Longlong and Chen, Jun and Deng, Jinxia and Wang, Na and Hong, Jiawang and Xing, Xianran},
abstractNote = {Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of -25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2- anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.},
doi = {10.1038/s41467-018-07526-x},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {Thu Nov 29 00:00:00 EST 2018},
month = {Thu Nov 29 00:00:00 EST 2018}
}
Web of Science
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